WO1982000288A1 - A process for removing cyanide ions from solutions - Google Patents

A process for removing cyanide ions from solutions Download PDF

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Publication number
WO1982000288A1
WO1982000288A1 PCT/SE1981/000205 SE8100205W WO8200288A1 WO 1982000288 A1 WO1982000288 A1 WO 1982000288A1 SE 8100205 W SE8100205 W SE 8100205W WO 8200288 A1 WO8200288 A1 WO 8200288A1
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WO
WIPO (PCT)
Prior art keywords
cyanide
solution
process according
electrolyte
electrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/SE1981/000205
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French (fr)
Inventor
N Soedermark
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Individual
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Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AU73261/81A priority Critical patent/AU7326181A/en
Publication of WO1982000288A1 publication Critical patent/WO1982000288A1/en
Priority to DK104682A priority patent/DK104682A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides

Definitions

  • the present invention relates to a process for removing cyanide ions from a cyanide-containing solution by anodic oxidation.
  • cyanide chemicals are used for different purposes resulting in liquid waste not allowable for disposal in available recipients. Therefore, the cyanide-containing liquid waste or solutions must be freed from their contents of cyanides before being discharged into recipients or municipal sewers. Examples of such industries are noble metal workshops, iron and steel industries, the photographic industries and surface finishing industries.
  • the present invention provides for a new process for removing cyanide ions from cyanide-containing solutions through which the disadvantages associated with the prior art are avoided or substantially reduced.
  • the pH of the solution is adjusted to a value of at least about 11 and the halide content of the solution shall be at least equivalent to the cyanide concentration.
  • the crux of the invention lies in the finding that when electrolysis is performed using intense agitation of the electrolyte the period of time required for full destruction of the cyanide ions will be substantially reduced. It has also been found that using the conditions outlined above results in deposition of solid carbon on the anode.
  • the technique of the invention enables treatment of any liquid waste containing cyanide ions.
  • electroplating baths containing 10-20 grams of cyanide per liter of solution can be efficiently treated using the process of the invention.
  • liquid waste containing smaller concentrations of cyanides may also be made harmless using the inventive technique.
  • agitation of the electrolyte by stirring same.
  • it is suitable to use a propeller to impart a rotary motion to the electrolyte.
  • the halide content of the solution is adjusted to about twice the equivalent of the cyanide concentration, and as a halide sodium chloride is preferred, but any alkali metal halide can be used, the chlorides being preferred.
  • the electrolysis is suitably performed using a current density of about 3-3.5 A per dm 2 , and to adjust the pH of the solution sodium hydroxide is the preferred choice of base.
  • the process of the present invention is used for rendering harmless the cyanide-containing waste solutions resulting from the recovery of noble metals in accordance with patent application No. filed simultaneously herewith, the cyanide ion removal can advantageously take place in the same electrolyzer.
  • new cathode plates are introduced into the electrolyzing vessel and the direction of current is reversed so that said plates become anodes onto which the deposition of carbon takes place. This will have for an effect that contamination of the walls of the electrolyzing vessel is avoided.
  • Fig. 1 shows an elevational side view of an electrolyzer for use in the process of the invention
  • Fig. 2 shows an elevational front view of the electrolyzer of Fig. 1;
  • Fig. 3 shows a top view of the electrolyzer of Fig. 1.
  • the electrolyzer shown is generally designated 1.
  • the electrolyzer 1 includes a vertical cylindrical vessel 3 attached to a fixture or stand 5.
  • Vessel 3 contains vertically extending anode plates 7 , 9, whereas the vessel 3 proper constitutes cathode.
  • Vessel 3 is connected to the negative electrode of a source of direct current, whereas the anode plates 7, 9 are attached to the positive electrode. All these features are conventional in the art and therefore not shown in the drawing.
  • Vessel 3 contains a centrally positioned propeller 11 connected by a shaft 13 to a motor 15 for its operation. At the lower end vessel 3 is provided with a discharge pipe 17.
  • the electrolyzing vessel 3 has a volume of about 300 liters and propeller 11 is positioned about 10 cm above the bottom of vessel 3. Vessel 3 of electrolyzer 1 is charged with about
  • the pH-value of the liquid is adjusted to about 11 and, furthermore, there is added about 1 % by weight of sodium chloride.
  • the contents of the vessel are electrolyzed using a current density of about
  • the primary advantage of the process of the invention lies in the short period of time necessary for complete electrolysis of the the cyanide-containing solution.
  • the period of electrolysis is usually of the order of several hours, for example 6 to 8 hours, whereas the technique of this invention enables complete electrolysis to be obtained within a fraction of an hour.
  • sodium chloride is preferred, as is sodium hydroxide for use as a base.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Removal Of Specific Substances (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Procede d'extraction d'ions cyanure d'une solution contenant du cyanure par oxydation anodique. Le pH de la solution est ajuste a au moins 11 environ et la teneur en halogenure est au moins equivalente a la concentration de cyanure. L'electrolyse s'effectue sous agitation intense en l'electrolyte pour obtenir un depot de carbone massif sur l'anode.Method for extracting cyanide ions from a solution containing cyanide by anodic oxidation. The pH of the solution is adjusted to at least about 11 and the halide content is at least equivalent to the concentration of cyanide. The electrolysis is carried out with intense stirring in the electrolyte to obtain a deposit of solid carbon on the anode.

Description

TITLE OF INVENTION:
A PROCESS FOR REMOVING CYANIDE IONS FROM SOLUTIONS.
TECHNICAL FIELD:
The present invention relates to a process for removing cyanide ions from a cyanide-containing solution by anodic oxidation.
In several industries cyanide chemicals are used for different purposes resulting in liquid waste not allowable for disposal in available recipients. Therefore, the cyanide-containing liquid waste or solutions must be freed from their contents of cyanides before being discharged into recipients or municipal sewers. Examples of such industries are noble metal workshops, iron and steel industries, the photographic industries and surface finishing industries.
BACKGROUND ART:
Up to now the cyanide-containing waste has been collected in destruction facilities within the plant, usually large basins, where destruction has taken place by oxidation with sodium hypochlorite. Small plants have to collect their wastes in closed vessels which have to be transferred to destruction plants with concomittant high costs. It is also known to destroy the cyanide contents of solutions by anodic oxidation, but the technology developed up to now has been complicated and requires long electrolyzing periods. Examples of the latter type of techniques are found in U.S. patent Ser.No. 3764,499, Swiss patent specification 444,066 and published Swedish patent application 77-12278-6.
SUMMARY OF THE INVENTION:
The present invention provides for a new process for removing cyanide ions from cyanide-containing solutions through which the disadvantages associated with the prior art are avoided or substantially reduced. In the process of the invention using anodic oxidation for destroying the cyanide ions the pH of the solution is adjusted to a value of at least about 11 and the halide content of the solution shall be at least equivalent to the cyanide concentration. The crux of the invention lies in the finding that when electrolysis is performed using intense agitation of the electrolyte the period of time required for full destruction of the cyanide ions will be substantially reduced. It has also been found that using the conditions outlined above results in deposition of solid carbon on the anode.
The technique of the invention enables treatment of any liquid waste containing cyanide ions. Thus, for example electroplating baths containing 10-20 grams of cyanide per liter of solution can be efficiently treated using the process of the invention. Of course, liquid waste containing smaller concentrations of cyanides may also be made harmless using the inventive technique.
It is preferred to provide the agitation of the electrolyte by stirring same. In providing for efficient stirring it is suitable to use a propeller to impart a rotary motion to the electrolyte. It is particularly preferred to provide for such intense agitation that air is sucked into the electrolyte. In addition to the fact that this will substantially shorten the period of time of electrolysis it also prevents uneven corrosion of the anode, particularly local corrosion at the interphase between surrounding air and electrolyte.
In a preferred embodiment of the invention the halide content of the solution is adjusted to about twice the equivalent of the cyanide concentration, and as a halide sodium chloride is preferred, but any alkali metal halide can be used, the chlorides being preferred.
The electrolysis is suitably performed using a current density of about 3-3.5 A per dm2, and to adjust the pH of the solution sodium hydroxide is the preferred choice of base.
When the process of the present invention is used for rendering harmless the cyanide-containing waste solutions resulting from the recovery of noble metals in accordance with patent application No. filed simultaneously herewith, the cyanide ion removal can advantageously take place in the same electrolyzer. In this case new cathode plates are introduced into the electrolyzing vessel and the direction of current is reversed so that said plates become anodes onto which the deposition of carbon takes place. This will have for an effect that contamination of the walls of the electrolyzing vessel is avoided.
EXAMPLE: The invention will be further illustrated in the following by a non-limiting specific example in conjunction with the appended drawing, wherein:
Fig. 1 shows an elevational side view of an electrolyzer for use in the process of the invention; Fig. 2 shows an elevational front view of the electrolyzer of Fig. 1; and
Fig. 3 shows a top view of the electrolyzer of Fig. 1.
In the drawing, the electrolyzer shown is generally designated 1. The electrolyzer 1 includes a vertical cylindrical vessel 3 attached to a fixture or stand 5. Vessel 3 contains vertically extending anode plates 7 , 9, whereas the vessel 3 proper constitutes cathode. Vessel 3 is connected to the negative electrode of a source of direct current, whereas the anode plates 7, 9 are attached to the positive electrode. All these features are conventional in the art and therefore not shown in the drawing. Vessel 3 contains a centrally positioned propeller 11 connected by a shaft 13 to a motor 15 for its operation. At the lower end vessel 3 is provided with a discharge pipe 17.
All parts of the electrolyzer 1 coming into contact with the solution or material to be electrolyzed are.made of acid-resistant steel.
In the instant example the electrolyzing vessel 3 has a volume of about 300 liters and propeller 11 is positioned about 10 cm above the bottom of vessel 3. Vessel 3 of electrolyzer 1 is charged with about
300 liters of cyanide-containing liquid waste. The contents of cyanide ions is about 2.5 g per liter- solution. The waste treated is the residual material remaining after noble metal recovery in accordance with the above-mentioned patent application filed simultaneously herewith.
By adding sodium hydroxide the pH-value of the liquid is adjusted to about 11 and, furthermore, there is added about 1 % by weight of sodium chloride. Under intense stirring with a propeller speed of about 900 revolutions per minute the contents of the vessel are electrolyzed using a current density of about
3-3.5 A/dm2 at a voltage of about 16 volts. After a period of time of 15 minutes practically all cyanide contents of the liquid had been oxidized and the anode plates 7, 9 were coated with a layer of pure carbon powder.
The primary advantage of the process of the invention lies in the short period of time necessary for complete electrolysis of the the cyanide-containing solution. In the conventional art the period of electrolysis is usually of the order of several hours, for example 6 to 8 hours, whereas the technique of this invention enables complete electrolysis to be obtained within a fraction of an hour.
It is to be noted that the invention is not delimited to the above example. Thus, as halides other substances than sodium chloride may be used. However, from a commercial point of view sodium chloride is preferred, as is sodium hydroxide for use as a base.

Claims

PATENT CLAIMS:
1. A process for removing cyanide ions from a cyanide-containing solution by anodic oxidation, the solution being adjusted to a pH of at least about 11 and to a halide content at least equivalent to the cyanide concentration, characterized thereby that electrolysis is performed under intense agitation of the electrolyte to result in deposition of solid carbon on the anode.
2. A process according to claim 1, characterized thereby that the agitation is provided by stirring the electrolyte.
3. A process according to claim 2, characterized thereby that a propeller is used to stir the electrolyte.
4. A process according to any preceding claim, characterized thereby that agitation is such that air is sucked into the electrolyte.
5. A process according to any preceding claim, characterized thereby that the halide content of the solution is adjusted to about twice the equivalent of the cyanide concentration.
6. A process according to any preceding claim, characterized thereby that sodium chloride is used to adjust the halide content of the solution.
7. A process according to any preceding claim, characterized thereby that the electrolysis is performed using a current density of about 3-3.5 A/dm 2.
8. A process according to any preceding claim, characterized thereby that sodium hydroxide is used to adjust the pH of the solution.
PCT/SE1981/000205 1980-07-11 1981-07-07 A process for removing cyanide ions from solutions Ceased WO1982000288A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU73261/81A AU7326181A (en) 1980-07-11 1981-07-07 A process for removing cyanide ions from solutions
DK104682A DK104682A (en) 1980-07-11 1982-03-10 PROCEDURE TO REMOVE CYANIDION FROM SOLUTIONS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8005138A SE8005138L (en) 1980-07-11 1980-07-11 SET TO CHARGE CYANIDES
SE8005138800711 1980-07-11

Publications (1)

Publication Number Publication Date
WO1982000288A1 true WO1982000288A1 (en) 1982-02-04

Family

ID=20341425

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1981/000205 Ceased WO1982000288A1 (en) 1980-07-11 1981-07-07 A process for removing cyanide ions from solutions

Country Status (9)

Country Link
US (1) US4417963A (en)
EP (1) EP0063123A1 (en)
JP (1) JPS57501068A (en)
CA (1) CA1173404A (en)
DK (1) DK104682A (en)
IT (1) IT1137723B (en)
NO (1) NO820777L (en)
SE (1) SE8005138L (en)
WO (1) WO1982000288A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4802995A (en) * 1987-06-05 1989-02-07 Rostoker, Inc. Method for decomposing the cyanide radical in cyanide-bearing wastes or materials
CN2063121U (en) * 1990-03-15 1990-10-03 杨新玉 Cyanogen removing purifier
US5288373A (en) * 1990-03-15 1994-02-22 Xinyu Yang Process of removing cyanide from waste water
US5230782A (en) * 1991-07-22 1993-07-27 International Business Machines Corporation Electrolytic process for reducing the organic content of an aqueous composition and apparatus therefore
US8093442B2 (en) * 2007-07-23 2012-01-10 Rio Tinto Alcan International Limited Electrochemical removal of dissociable cyanides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH444066A (en) * 1961-02-13 1967-09-15 Kampschulte & Cie Dr W Process for the decomposition of toxic cyano compounds in liquids and device for carrying out the process
SE321836B (en) * 1968-06-19 1970-03-16 Nordarmatur Ab
US3764499A (en) * 1970-11-26 1973-10-09 K Okubo Process for removal of contaminants from wastes
GB1362704A (en) * 1967-09-18 1974-08-07 Roy C H Electrolytic purification process and apparatus

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773025A (en) * 1953-09-10 1956-12-04 Westinghouse Electric Corp Destroying cyanides in aqueous cyanide solutions
US3764497A (en) * 1971-04-14 1973-10-09 Hooker Chemical Corp Decreasing cyanide content by an electrochemical technique
US4029557A (en) * 1975-10-15 1977-06-14 Thiokol Corporation Treatment of water containing cyanide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH444066A (en) * 1961-02-13 1967-09-15 Kampschulte & Cie Dr W Process for the decomposition of toxic cyano compounds in liquids and device for carrying out the process
GB1362704A (en) * 1967-09-18 1974-08-07 Roy C H Electrolytic purification process and apparatus
SE321836B (en) * 1968-06-19 1970-03-16 Nordarmatur Ab
US3764499A (en) * 1970-11-26 1973-10-09 K Okubo Process for removal of contaminants from wastes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Gmelins Handbuch der Anorganischen Chemie, Kohlenstoff, Teil B-Lieferung 2, Weinheim 1968 p. 788, lines 10-8 from the bottom. *
Industrial Water Engineering Vol. 17, no. 2 (1980) p. 28-30. C.P.C. Poon, K.P. Soscia "A process for simultaneous removal of cadmium and cyanide". *

Also Published As

Publication number Publication date
IT1137723B (en) 1986-09-10
NO820777L (en) 1982-03-10
CA1173404A (en) 1984-08-28
SE8005138L (en) 1982-01-12
JPS57501068A (en) 1982-06-24
EP0063123A1 (en) 1982-10-27
IT8122869A0 (en) 1981-07-10
US4417963A (en) 1983-11-29
DK104682A (en) 1982-03-10

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